CN110882712A - Method for preparing silicide catalyst by pyrolyzing metal organic polymer - Google Patents

Method for preparing silicide catalyst by pyrolyzing metal organic polymer Download PDF

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Publication number
CN110882712A
CN110882712A CN201911249158.1A CN201911249158A CN110882712A CN 110882712 A CN110882712 A CN 110882712A CN 201911249158 A CN201911249158 A CN 201911249158A CN 110882712 A CN110882712 A CN 110882712A
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organic polymer
catalyst
pyrolysis
silicide catalyst
preparing
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梁长海
韩树华
陈霄
李闯
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Jinzhou Kaiten Technology Co Ltd
Dalian University of Technology
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Jinzhou Kaiten Technology Co Ltd
Dalian University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J27/224—Silicon carbide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention belongs to the field of fine chemical engineering, and discloses a method for preparing a silicide catalyst by pyrolyzing a metal organic polymer. Modifying and modifying the silicon-containing organic polymer on a molecular level by utilizing metal salt, and introducing transition metal elements such as Fe, Co, Ni and the like into a framework of the pyrolysis precursor. Under a certain reduction temperature, the metal silicide catalyst with uniform particle size, good dispersibility, higher catalytic selectivity and catalytic stability can be prepared. The preparation method is simple and safe in preparation process, the catalyst is small in particle size and uniform in distribution, and the obtained silicide catalyst has high catalytic activity and stability for preparing the aromatic imine and the derivative thereof through series catalysis.

Description

Method for preparing silicide catalyst by pyrolyzing metal organic polymer
Technical Field
The invention belongs to the field of fine chemical engineering, and relates to a preparation method of a silicide catalyst prepared by pyrolysis of a metal organic polymer and application of the silicide catalyst in series catalytic reaction of nitroaromatic hydrocarbon and ketone or aldehyde serving as raw materials to obtain aromatic imine and derivatives thereof.
Background
The aromatic imine and the derivative thereof play a central role in organic synthesis, and various surfactants, detergents and dyes which are common in daily life and various additives in the petrochemical industry can not leave the figure of the aromatic imine and the derivative thereof. Generally, aromatic imines and their derivatives are prepared by the condensation of ketones or aldehydes with amines, which are often based on the selective reduction of nitroarenes. The aromatic imine and the derivative thereof are prepared by directly taking nitroaromatic and ketone or aldehyde as raw materials through series catalysis, thereby avoiding the separation and purification of intermediate products and greatly improving the chemical synthesis efficiency.
In the past, some noble metal (Au, Pt, Ru, Ir-Pd) catalysts for preparing aromatic imine and derivatives thereof by serial catalysis using nitroaromatic hydrocarbons and ketone or aldehyde as raw materials have been reported, but with the increasing exhaustion of earth resources, the widespread use of noble metal catalysts does not conform to the green chemical concept of sustainable development, and therefore, the development of a non-noble metal catalyst with high activity and high stability is urgently needed.
Transition metal silicide catalysts are the most promising alternatives to noble metal catalysts. The metal silicide is a substance formed by entering silicon atoms into metal lattices, and the insertion of the silicon atoms can adjust the electronic structure and the geometric structure of metal active sites, improve the catalytic selectivity and the stability of the metal silicide and enable the metal silicide to show the properties similar to noble metals.
Typical production methods include liquid phase sintering, powder metallurgy, ultra-high pressure hot isostatic pressing, spark plasma sintering, etc., but these methods require extremely high temperatures and pressures to achieve highly dispersed, dense nanostructured catalytic materials, and further, these methods often require the use of nano-sized ceramic powders as starting materials, which introduce undesirable contaminants.
Disclosure of Invention
The invention provides a method for preparing a silicide catalyst by pyrolyzing a metal organic polymer. Aiming at the synthesis of the prior non-noble metal catalyst, a simple and effective preparation method is provided, and the metal salt is utilized to modify and modify the silicon-containing organic polymer on the molecular level, so that transition metal elements such as Fe, Co, Ni and the like are introduced into the framework of the pyrolysis precursor. Under a certain reduction temperature, the metal silicide catalyst with uniform particle size, good dispersibility, higher catalytic selectivity and catalytic stability can be prepared. Compared with other methods, the method has the advantages of relatively mild preparation conditions, safe, simple and convenient operation, and can realize in-situ reduction of the catalyst and overcome the defect that the catalyst is oxidized after contacting with air so as to lose catalytic activity.
The technical scheme of the invention is as follows:
a method for preparing a silicide catalyst by pyrolyzing a metal organic polymer comprises the following steps:
(1) dissolving metal salt and silicon-containing organic polymer in tetrahydrofuran or xylene solvent according to the mass ratio of 1:2.5-1:20, heating and stirring for 2-15 h at the temperature of 50-180 ℃, and removing the solvent by adopting a vacuum pumping or high-temperature blowing method to obtain a corresponding metal organic polymer pyrolysis precursor;
(2) crosslinking and curing the metal organic polymer pyrolysis precursor at 100-220 ℃ for 1-8 h, and then mixing the metal organic polymer pyrolysis precursor with a solvent in a volume ratio of 1: 2H2And (3) carrying out temperature programmed pyrolysis at 400-1000 ℃ at the temperature rise rate of 5 ℃/min under the mixed gas of Ar to obtain the silicide catalyst.
The metal salt is one of ferric chloride, cobalt chloride, nickel chloride, ferric acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate, cobalt acetate and nickel acetate.
The silicon-containing organic polymer is polysilazane or polydimethylsilane.
The silicide catalyst is Fe3Si/SiC、Ni2Si/SiC、CoSi/SiC、Ni2Si/SiCN, CoSi/SiCN and Fe3Si/SiCN.
The prepared silicide catalyst is mainly used for preparing aromatic imine and derivatives thereof by directly taking nitroaromatic and ketone or aldehyde as raw materials and carrying out serial catalytic reaction.
The invention has the beneficial effects that: the preparation method is safe and simple in preparation process, the catalyst is small in particle size and uniform in distribution, and the prepared silicide catalyst has high selective hydrogenation performance and hydrogenation stability for preparing the aromatic imine and the derivative thereof through series catalysis.
Drawings
FIG. 1 shows Ni as a product of the present invention2XRD analysis result pattern of Si/SiCN.
FIG. 2 shows Ni2The product selectivity diagram of aromatic imine and its derivatives prepared by Si/SiCN serial catalysis.
FIG. 3 shows Ni2And (3) a stability chart of series coupling of nitrobenzene and benzaldehyde catalyzed by Si/SiCN.
Detailed Description
The present invention will be described in detail below by way of examples, which are illustrative only and are not intended to limit the present invention thereto.
Example 1
Adding 0.85g of nickel acetate and 5.12g of organic polysilazane into 50mL of anhydrous and oxygen-free tetrahydrofuran, uniformly stirring, heating and stirring at 70 ℃ for 4h, and then vacuumizing and removing solvent tetrahydrofuran at 50 ℃ to obtain the viscous metal Ni modified metal organic polymer pyrolysis precursor. 0.5-2.0g of the pyrolyzed precursor was heated in an oil bath at 150 ℃ for 5H and then transferred to a tube furnace in H2Mixing with Ar (H)2Ar is 1:2), staying at 1000 deg.C for 2h, proceeding programmed heating pyrolysis, and coolingAfter the temperature is reduced to room temperature, the catalyst is taken out and ground to obtain Ni2Si/SiCN catalyst.
The XRD analysis results of this sample are shown in fig. 1.
Example 2
Adding 0.52g of ferric acetylacetonate and 7.55g of organic polysilazane into 50mL of anhydrous and oxygen-free tetrahydrofuran, uniformly stirring, heating and stirring at 140 ℃ for 6h, and then heating and purging at 80-100 ℃ to remove solvent tetrahydrofuran, thereby obtaining the viscous metal Fe modified metal organic polymer pyrolysis precursor. Taking 0.5-2.0g of pyrolysis precursor to carry out temperature programmed pyrolysis in a tubular furnace, and carrying out H2Mixing with Ar (H)2Ar is 1:2), firstly staying at 200 ℃ for 1.5h, then staying at 1000 ℃ for 3h, cooling to room temperature, taking out the catalyst and grinding to obtain Fe3Si/SiCN catalyst.
Example 3
Adding 0.63g of nickel chloride and 3.05g of organic polydimethylsilane into 20mL of anhydrous and oxygen-free xylene, heating and stirring at 50 ℃ for 12h, and then removing the xylene solvent at 70-90 ℃ in vacuum to obtain the viscous metal Ni modified metal organic polymer pyrolysis precursor. Taking 0.5-2.0g of pyrolytic precursor in a tube furnace in H2Mixing with Ar (H)2Ar is 1:2), the temperature programmed pyrolysis is carried out, firstly the pyrolysis is kept for 2h at 200 ℃, then the pyrolysis is kept for 4h at 1000 ℃, the catalyst is taken out and ground after the temperature is reduced to the room temperature, and the Ni is obtained2A Si/SiC catalyst.
Example 4
0.64g of cobalt acetate and 0.12g of dicumyl peroxide are added into 40mL of anhydrous and oxygen-free xylene, after uniform stirring, 2.43g of organic polydimethylsilane is added, heating and stirring are carried out at 50 ℃ for 14h, then solvent xylene is pumped out at vacuum 50-60 ℃, and the viscous metal Co modified metal organic polymer pyrolysis precursor is obtained. Taking 0.5-2.0g of pyrolytic precursor in a tube furnace in H2Mixing with Ar (H)2Ar is 1:2), temperature programmed pyrolysis is carried out, the temperature is kept for 4 hours at 900 ℃, the catalyst is taken out and ground after the temperature is reduced to the room temperature, and the CoSi/SiC catalyst is obtained.
Example 5
Nickel silicide (Ni) prepared in example 12The catalytic performance of the Si/SiCN) catalyst in the reaction for preparing the aromatic imine and the derivative thereof by series catalysis is researched, and the reaction is carried out in a high-temperature high-pressure kettle type reactor.
The reaction conditions are as follows: 0.1g of catalyst (Ni)2Si/SiCN), 0.123g of nitrobenzene, 0.212g of benzaldehyde, reaction pressure 3MPaH2The reaction temperature was 150 ℃. The product analysis adopts gas chromatography and a hydrogen flame detector. Before the reaction starts, Ni2The Si/SiCN catalyst is firstly H in a tube furnace2Mixed atmosphere with Ar (H)2Ar ═ 1:2), reduced at 400 ℃ for 2h, and then passivated overnight under a pure Ar atmosphere. Mainly investigating Ni2The catalytic hydrogenation performance and the stability of Si/SiCN. The reaction result shows that Ni2Si/SiCN can catalyze nitrobenzene and benzaldehyde in series to generate aromatic imine and derivatives thereof with high selectivity, the conversion rate of nitrobenzene can reach 99%, and the selectivity of target products of aromatic imine and derivatives thereof can reach about 90% (as shown in figure 2). After 5 cycles of reaction, Ni2Si/SiCN still has excellent catalytic activity and selectivity (as shown in figure 3).
Example 6
The catalytic performance of the cobalt silicide (CoSi/SiC) catalyst prepared in example 4 in the reaction for preparing aromatic imine and its derivatives by tandem catalysis was studied, and the reaction was carried out in a high temperature autoclave reactor.
The reaction conditions are as follows: 0.1g of catalyst (CoSi/SiC), 0.123g of nitrobenzene, 0.212g of benzaldehyde, reaction pressure 5MPaH2The reaction temperature was 120 ℃. The product analysis adopts gas chromatography and a hydrogen flame detector. Before the reaction starts, the CoSi/SiC catalyst is firstly H in a tube furnace2Mixed atmosphere with Ar (H)2Ar ═ 1:2), reduced at 400 ℃ for 2h, and then passivated overnight under a pure Ar atmosphere. The result shows that CoSi/SiC can efficiently catalyze nitrobenzene and benzaldehyde to directly prepare aromatic imine and derivatives thereof in a serial catalysis manner, the conversion rate of nitrobenzene can reach 99%, and the selectivity of the target product can reach about 95%.

Claims (5)

1. A method for preparing a silicide catalyst by pyrolyzing a metal organic polymer is characterized by comprising the following steps:
(1) dissolving metal salt and silicon-containing organic polymer in tetrahydrofuran or xylene solvent according to the mass ratio of 1:2.5-1:20, heating and stirring for 2-15 h at the temperature of 50-180 ℃, and removing the solvent by adopting a vacuum pumping or high-temperature blowing method to obtain a corresponding metal organic polymer pyrolysis precursor;
(2) crosslinking and curing the metal organic polymer pyrolysis precursor at 100-220 ℃ for 1-8 h, and then mixing the metal organic polymer pyrolysis precursor with a solvent in a volume ratio of 1: 2H2And (3) carrying out temperature programmed pyrolysis at 400-1000 ℃ at the temperature rise rate of 5 ℃/min under the mixed gas of Ar to obtain the silicide catalyst.
2. The method for preparing silicide catalyst by pyrolysis of organometallic polymer according to claim 1 wherein the metal salt is one of ferric chloride, cobalt chloride, nickel chloride, ferric acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate, cobalt acetate and nickel acetate.
3. The method for preparing silicide catalyst by pyrolysis of organometallic polymer according to claim 1 or 2 wherein the silicon-containing organic polymer is polysilazane or polydimethylsilane.
4. The method for preparing silicide catalyst by pyrolysis of metal organic polymer according to claim 1 or 2, wherein the prepared silicide catalyst is Fe3Si/SiC、Ni2Si/SiC、CoSi/SiC、Ni2Si/SiCN, CoSi/SiCN and Fe3Si/SiCN.
5. The method for preparing silicide catalyst by pyrolysis of metal organic polymer as claimed in claim 3, wherein the prepared silicide catalyst is Fe3Si/SiC、Ni2Si/SiC、CoSi/SiC、Ni2Si/SiCN, CoSi/SiCN and Fe3Si/SiCNOne kind of (1).
CN201911249158.1A 2019-12-09 2019-12-09 Method for preparing silicide catalyst by pyrolyzing metal organic polymer Pending CN110882712A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001014060A2 (en) * 1999-08-25 2001-03-01 Massachusetts Institute Of Technology Surface-confined catalytic compositions
CN101371986A (en) * 2008-05-15 2009-02-25 大连理工大学 Method for preparing Cu-Cr metallic oxide with high specific surface area and application
CN102245688A (en) * 2008-10-20 2011-11-16 3M创新有限公司 Electrically conductive composite material and thermoelectric device using electrically conductive polymer material
CN102247848A (en) * 2011-05-23 2011-11-23 大连理工大学 Transition metal silicide catalyst for hydrodesulfurization and preparation method thereof
CN102600877A (en) * 2012-01-11 2012-07-25 大连理工大学 High-selectivity catalyst for naphthalene hydrogenation reaction for preparing tetrahydronaphthalene and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001014060A2 (en) * 1999-08-25 2001-03-01 Massachusetts Institute Of Technology Surface-confined catalytic compositions
CN101371986A (en) * 2008-05-15 2009-02-25 大连理工大学 Method for preparing Cu-Cr metallic oxide with high specific surface area and application
CN102245688A (en) * 2008-10-20 2011-11-16 3M创新有限公司 Electrically conductive composite material and thermoelectric device using electrically conductive polymer material
CN102247848A (en) * 2011-05-23 2011-11-23 大连理工大学 Transition metal silicide catalyst for hydrodesulfurization and preparation method thereof
CN102600877A (en) * 2012-01-11 2012-07-25 大连理工大学 High-selectivity catalyst for naphthalene hydrogenation reaction for preparing tetrahydronaphthalene and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GUAN JINGCHAO ET AL: ""Preparation and size-dependent magnetism of highly dispersed iron silicide nanoparticles on silica"", 《JOURNAL OF MATERIALS CHEMISTRY C》 *
XIAO CHEN ET AL: ""Intermetallic Ni2Si/SiCN as a highly efficient catalyst for the one-pot tandem synthesis of imines and secondary amines"", 《INORGANIC CHEMISTRY FRONTIERS》 *

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Application publication date: 20200317